Derivatives of rosin amines



United States Patent DERIVATIVES 0F RQ N Albert J.v 'Saukaitis, Wayne,and George S'. Gardner, Elkins Park, Pa., assignors to. AmericanChemical Paint Company, Ambler, Pa., a corporation of Delaware NoDrawing. Application June 10, 1953, Serial No. 360,814

14 Claims. (Cl. 25'28.55)

This invention relates to new chemical compounds which may be describedas derivatives of rosin amine-s. They are represented by the formulawhere R is a radical selected from the group consisting of abietyl,hydroabietyl and dehydroabietyl, Y is the gnoup, .CHaRr, X is a radicalselected from the group consisting of hydrogen and CHz.R1, and Rrepresents alpha k tcny r up The compounds which we have developed havebeen found to be exceptionally strong, long-lived corrosion inhibitorsand are of particular value as inhibitors in acid mediums or bath-s forthe prevention or retardation of the attack of such baths upon metalsurfaces and especially upon steel surfaces.

The principal objects of our invention are to provide new chemicalcompounds of the character described which are especially useful asinhibitors of acid corrosion when used i-n acid baths which aremaintained at ordinary roorn or living temperatures or at temperatureshigher" than average room or living temperatures; to provide cornpoundswhich are particularl fiicient when used with hydrochloric acid inoil-well acidiz e; o previ e su h ccmpaunds which can be prepared n a smple manner from easily obtainable low cost raw materials; o-providecompounds of the character described which have an. unusual-l-y highdegree of heat stability, the cpmpouuds of the pre nt invention having eni nd o e veryeilecr tive as inhibitors even up to temperatures a h ghas 1-5Q Cr; and, in general, to improve the usefulnessand lower the.cost of inhibiting materials for a wide variety of industrial oprations... r ex mp we a f und that the materials of our invention arehighly useful for the protection of metals generally. andpanticularlyfor me protection of ferriferous metals during theremovalqof water-borne deposits, of heat scale and of rust whercitheremoval is carried out by means of acid salts or acids such ashydrochloric, sulfuric, aceti formic and the, like. Our inventionresults in the conservation of large gnan titiesof-metals as-well as ofacids.

The materials of ur inv ntion may be prep ed by reacting rosin amine,formaldehyde and a ketone. The term rosin amine as used hereindesignates those primary amines which are made from mosins or rosinamines and they may be considered as broadly including'compoundscontaining the abietyl, hydroabietyl and dehydroabietyl radicals.Furthermore, the term is to be considered as covering primary aminesderived from rosin and resin acids whether or not modified "byhydrogenation for dehydrog ena-tion. l

2,758,970 Patented Aug. 14, 195.6

Acetone Methyl: ethyl ketone Diaeetone alcohol Berna-he dicu i 2.,4 Aceenyln ace one- Isophorone Mesityl oxide gy lopentanone cy lohexanoneAeetophenche g n al, k ones. o a l ke natu e a a l u eih itsater als frm which he impro d c mmends m y be reua d A e ny ientmeth fo fiec n heeac ion equired o produce our no ma e ials. s as ollo s: One 1 19 of.resin am ne: is c ed h to four. mo es at an app opriate ketche plu one ofour m of orthaldehyd G neral y; he s n amine i issolved n h appropriateetone ter which. from Que t fou mole of 37% aqueous formaldehydesolution is added. with stirring. We prefer to bring about the reactionof this mixture in an acid medium and to this end one mole ofconcentrated hydrochloric acid is added with "stirring under refluxconditions. The mixture is then allowed to. reflux for a period varyingbetween one. and twentyrfour hours. At the end of the. reflux period, ifa volatile ketone. has been us,ed:,.anyex.c.ess. ketone isdistilled.oif. On the other hand, if a Katrine having a high boiling point. hasbeen u ed, he. Quant ty of ke ne adde may be conveniently ri'. d to.that: which. is consumed in the r action so, tha 9a o ketene i neces ryat he e d of the re ux. period-v he reaction mix ure, wh prepa ed asabove dc,- seri d, will contain he mno hd f th -pie at i vear n inhe tem o their h d eehlcrides and? hese compounds may be used as inhibiting,materials without further purification or modification. Quite often thereaction product is soluble in water or mineral acid but if not sosoluble it may be fopmulated into, useful inhibitor compcsi ien ei h bymea or ppropr te s l en such as a ccho r by means. r d sp in a e t o iother ay-s n wn to he a e ha e found tha certain modification ,of the abve g ral pro ed re may be adopted if d redcr ins a c ds he han hY QhlQfi ac d ay h u ed s f e mpehydr b mic ac d a ti acid or. T. acid n P c fWater he s i able ol ent su h a alcohol may be employed andparaformaldehyde maybe used instead of the aqueous solution offormaldehyde referred to.

With the understanding that R is a radical selected tr th. the groupceusisting of ,abietyl, hydroabietyl and .dehydrea ie yl. formation. ofthe comp ef'the P e ent invention may be illustrated by the: following:reactions:

(, rmninciq none c ne Ofifia unnememo 0.0111,]101 (2) R:NHQ.H\CL+ monozonio'oons onetime-0cm an ,noi qH ig-llgio O .QHs;

In these reactions, acetone has been used as an example of a ketone.Other ketones may be used. If, forexample, cyclohexanone had been usedin Equation 1 instead of acetone, the alpha-ketonyl group which appearsabove would be alpha-cyclohexanonyl:

II C H instead of acetonyl:

--CH2.CO.CH3

Thus, it may be said that the compounds of the present invention may besummarized in terms of the general formula given at the beginning ofthis specification. These compounds are secondary or tertiary amines andshow the characteristic properties of such compounds. For example, theyform salts with acids and, as previously indicated, are convenientlyused in the form of acid salts.

As has been stated, the compounds of the present invention are useful bythemselves as inhibitors. However, it is quite customary in this art attimes, if desirable, to prepare inhibitor formulations which make use ofmore than just one ingredient. Our compositions lend themselvesexceptionally well to such formulations. For instance, they may beadmixed with soluble copper salts, thiourea, etc.

Example 1 In a round-bottom Pyrex flask is placed 217 grams of acommercial grade of dehydrogenated rosin amine (approximately 0.70mole). Four moles (293 ml.) of acetone are added, and 2.2 moles (163m1.) of 37% solution of formaldehyde. The mixture is stirred slowly witha mechanical stirrer, and 0.70 mole (70 ml.) of 20 B. hydrochloric acidis added in small increments over a period of minutes. The mixture isrefluxed gently for hours. At the end of this time, the liquid is distilled to a vapor temperature of 90 C., 200 ml. of distillate beingobtained. The distillate contains the excess acetone plus some water andformaldehyde. The residue in the flask consists principally of asolution of:

CHz.CH2.CO.CHg

R-N .HCl CHz.CHz.CO.CH3 which is a dark, oily, viscous material. Thematerial may be used without further modification. However, we havefound it useful to dilute it with water in order to prepare a rather lowviscosity inhibitor formulation. Consequently, the inhibitor formulationof Example 1 is obtained by diluting the product just prepared withwater to make up a total weight of 620 grams. This solution is wellmixed and is now ready for use as an inhibitor.

Example 2 Proceed according to the instructions contained in Example 1but add to the final inhibiting product an equal volume of a copperchloride solution of 7.5 grams of copper chloride in 100 ml. of water.

Example 3 In a Pyrex flask is placed 315 grams of a commercial mixtureof rosin amine, the major constituent of which is dehydroabietylamine,the remaining portion being dihydro and tetrahydroabietylamine. 2.00moles of acetone and 2.5 moles of aqueous formaldehyde are added. Themixture is stirred slowly with a mechanical stirrer, and 1.0 mole (100m1.) of B. hydrochloric acid is added slowly. The mixture is boiledgently under reflux for 24 hours. This material has a compositionconsisting principally of:

CH:.CH2.CO.CH3

At the end of 24 hours reflux period, suflicient water is added to makeup a total weight of 900 grams and this represents the completedcorrosion inhibitor formulation of Example 3.

Example 4 grams of pentanedione 2,4, 217 grams of commercial grade ofrosin amine, 92 ml. of 37% formaldehyde solution, and 100 ml. of 20hydrochloric acid are mixed in a reaction flask. The solution isrefluxed for one hour, during which two layers are formed. The mixtureis poured into a separatory funnel and the dark, viscous, liquid whichforms the bottom layer is separated from the supernatant aqueous layer.The product is largely soluble in water, although it has already beenseparated from an aqueous layer. The product is the corrosion inhibitor,and can be blended into formulations containing wetting agents,alcohols, or other appropriate solvents.

Example 5 196 grams of mesityl oxide, 217 grams of commercial grade ofrosin amine, and 163 ml. of 37% aqueous formaldehyde solution are placedin a reaction flask. 100 ml. of 20 hydrochloric acid is added, slowly.The mixture is refluxed 2 hours. The mixture, now consisting of twolayers, is allowed to settle two days. The lower layer is separated.This is the corrosion inhibitor.

Example 6 217 grams of commercial grade of rosin amine, 232 grams ofdiacetone alcohol, 163 ml. of aqueous formaldehyde solution, 37% byweight, and 100 ml. of 20 hydrochloric acid solution are mixed in areaction flask. At the beginning of the reaction the mixture ishomogeneous. After refluxing 15 hours the mixture separates into twolayers. The lower, oily layer is separated. This is the corrosioninhibitor.

Example 7 217 grams of a commercial mixture of rosin amines, the majorconstituent of which is dehydroabietylamine, is dissolved in 144 g. (2.0moles) of methyl ethyl ketone. I-Iydrobromic acid (Sp. Gr. 1.5), grams,is added slowly, with stirring. The solution is refluxed gently, and 75grams of paraformaldehyde are added slowly, over a period of threehours. 100 ml. of a suitable solvent such as isopropanol is added, andthe solution is then refluxed over night. The finished solution weighed650 grams. This is the corrosion inhibitor.

In order to evaluate the compounds of the present invention ascommercial inhibitors, a solution of mls. of 10 B. hydrochloric acid wasplaced in a Pyrex test tube (1 /z 8) and 0.5% by volume of the inhibitorwas suspended or dissolved therein. The test tube and contents wereimmersed in a thermostatic bath maintained at F. After the contents ofthe tube reached 180 F., a piece of descaled hot rolled steel strip /z"10" 0.03") was folded in half and placed in the solution. The tube wasthen immediately connected to a device by means of which the evolvedhydrogen could be collected and measured. The volume of hydrogencollected was corrected to 0 C. and 760 mm. pressure. The volume ofhydrogen evolved in three hours is the figure used in calculating thestrength rating. The strength rating is given by the formula:

Volume of hydrogen collected in three hours 100, 204 88, 85, 64, 44 and127. From this it may be seen that the compounds of the presentinvention have exceptional inhibiting value.

The comparisons just given were made in such a way as to simulateoil-well acidizing conditions as closely as possible in the laboratoryin an effort to give a practical evaluation of the usefulness of thecompounds of the present invention.

It is difficult to specify the exact amount of the compounds of thepresent invention to be used to inhibit the attack of corrosive fluidsupon metals. At times as little as 0.01% by weight may be needed. Atother times it may be more or less, depending on the job to be done.Suflice it to say, enough material to accomplish the desired result is amatter which may be determined by means of simple test in various waysfamiliar to the art.

While the detailed description of the invention has been made withspecific emphasis on its utility with ferriferous metal surfaces, itshould be emphasized that the inhibitors are not limited to use withsteel. For instance, the materials are useful in reducing the rate ofcorrosion of metals such as magnesium, aluminum and zinc when they areexposed to the'action of a corrosive material such as hydrochloric acid.

We claim:

1. As a new material, a chemical compound represented by the formulawhere R is a radical selected from the group consisting of abietyl,hydroabietyl and dehydroabietyl, Y is the group CH2.R' X is a radicalselected from the group consisting of hydrogen and CH2.R1, and R1represents alpha ketonyl groups.

2. As a new material, the product formed by the reaction, in thepresence of acid, between rosin amine, a ketone having a reactivehydrogen atom adjacent to the carbonyl group and formaldehyde.

3. As a new material, the product formed by the reaction, in thepresence of acid, between rosin amine, a ketone having a reactivehydrogen atom adjacent to the carbonyl group and formaldehyde in a molarratio of approximately 1 rosin amine, 1 to 4 ketone and 1 to 4formaldehyde.

4. The method of making an inhibitor which comprises reacting, in thepresence of acid, a mixture of a rosin amine, a ketone having a reactivehydrogen atom adjacent to the carbonyl group and formaldehyde.

5. The method of claim 4 wherein the mixture contains 1 mole of therosin amine to 1 to 4 moles each of the ketone and the formaldehyde.

6. The method of claim 4 in which the acid is hydrochloric acid.

7. The method of claim 4 in which the acid is chosen from the groupconsisting of hydrochloric, hydrobromic, acetic and sulfuric acids.

8. The method of making an inhibitor comprising admixing under reactiveconditions in the following proportions 1 mole of rosin amine with 1 to4 moles of a ketone having a reactive hydrogen atom adjacent thecarbonyl group and 1 to 4 moles of formaldehyde in an aqueous solutionwhich contains at least 1 mole of hydrochloric acid.

9. The method of claim 8 in which the reaction takes place under refluxconditions and over a period of approximately 1 to 24 hours.

10. The method of making an inhibitor which com- 1 In this test the acidsolution contained in addition to 0.5% by volume of the formulation ofExample 1, 0.0375% wt./vl. copper chloride.

prises preparing a solution of 1 mole of rosin amine and from 1 to 4moles of ketone from the group consisting of:

Acetone Isophorone Methyl ethyl ketone Mesityl oxide Diacetone alcoholCyclopentanone Pentane dione, 2, 4 Cyclohexanone Acetonyl acetoneAcetophenone and from 1 to 4 moles of ketone from the group consistingof:

Acetone Isophorone Methyl ethyl ketone Mesityl oxide Diacetone alcoholCyclopentanone Pentane dione, 2,4 Cyclohexanone Acetonyl acetoneAcetophenone adding to the solution from 1 to 4 moles of an aqueousformaldehyde solution accompanied with stirring, adding with stirringapproximately 1 mole of hydrochloric acid, refluxing the mixture forfrom 1 to 24 hours, and separating the lighter aqueous portion to leavea residue of inhibiting material.

12. The method of making an inhibitor which comprises reacting a mixtureof rosin amine, a ketone and formaldehyde, the reaction taking place inan aqueous acid solution chosen from the group consisting ofhydrochloric, hydrobromic, acetic and sulfuric acids and the ketonebeing chosen from the group consisting of:

Acetone Isophorone Methyl ethyl ketone Mesityl oxide Diacetone alcoholCyclopentanone Pentane dione, 2,4 Cyclohexanone Acetonyl acetoneAcetophenone 13. The method of controlling metal corrosion caused by anacidic medium which consists in adding to the medium a quantity of acompound having the formula where R is a radical selected from the groupconsisting of abietyl, hydroabietyl and dehydroabietyl, Y is the groupCH2.R1, X is a radical selected from the group consisting of hydrogenand CH2.R1, and R1 represents alpha ketonyl groups, the quantity addedbeing suflicient to materially reduce the rate of corrosion.

14. An aqueous :acidic treating solution containing a compound havingthe following formula where R is a radical selected from the groupconsisting of abietyl, hydroabietyl and dehydroabietyl, Y is the groupCH2.R1, X is a radical selected from the group consisting of hydrogenand CI-Iz.R1, and R1 represents alpha ketonyl groups, the quantity ofwhich compound present being sufiicient to materially reduce thecorrosive attack of the solution on metal.

References Cited in the file of this patent UNITED STATES PATENTS1,877,504 Grebe et al Sept. 13, 1932 2,489,668 Plati Nov. 29, 19492,511,064 Ingram June 13, 1950 2,564,759 Haggard Aug. 21, 1951 2,649,415Sundberg et a1. Aug. 18, 1953

1. AS A NEW MATERIAL, A CHEMICAL COMPOUND REPRESENTED BY THE FORMULA 13.THE METHOD OF CONTROLLING METAL CORROSION CAUSED BY AN ACIDIC MEDIUMWHICH CONSISTS IN ADDING TO THE MEDIUM A QUANTITY OF A COMPOUND HAVINGTHE FORMULA